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| United States Patent |
5,512,621
|
|
Pastor
, et al.
|
April 30, 1996
|
Alpha crystalline modification of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-t'-biphenyl-2,2'-diyl)
phosphite!
Abstract
The alpha crystalline modification of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite! is obtained by crystallizing said compound from selected
solvents, preferably from a mixture of an aromatic hydrocarbon solvent and
a lower alkanol.
The alpha crystalline form is an effective process stabilizer for
polyolefins, particularly polypropylene.
| Inventors:
|
Pastor; Stephen D. (Danbury, CT);
Shum; Sai P. (Pleasantville, NY);
Odorisio; Paul A. (Leonia, NJ)
|
| Assignee:
|
Ciba-Geigy Corporation (Ardsley, NY)
|
| Appl. No.:
|
152106 |
| Filed:
|
November 12, 1993 |
| Current U.S. Class: |
524/119; 252/400.21; 508/305; 508/422; 524/111; 554/4; 558/78 |
| Intern'l Class: |
C07F 009/145; C08K 005/527 |
| Field of Search: |
524/119
558/78
|
References Cited
U.S. Patent Documents
| 4318845 | Mar., 1982 | Spivack et al. | 524/91.
|
| 4374219 | Feb., 1983 | Spivack et al. | 524/91.
|
| Foreign Patent Documents |
| 0026893 | Apr., 1981 | EP.
| |
Other References
L.C. Cross,et al. Pure Appl. Chem 45, 11-30 (1976).
G. Gold, et al., J. Pharm. Sci., 55, 1291 (1966).
|
Primary Examiner: Ramsuer; Robert W.
Assistant Examiner: Ambrose; Michael G.
Attorney, Agent or Firm: Hall; Luther A. R.
Parent Case Text
This is a continuation-in-part of application Ser. No. 07/983,180, filed on
Nov. 30, 1992, now U.S. Pat. No. 5,334,739, issued Aug. 2, 1994.
Claims
What is claimed is:
1. The alpha, monoclinic crystalline form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite!, characterized by melting in the range of
145.degree.-165.degree. C. and by an X-ray diffraction pattern exhibiting
lines of very high intensity at 5.2; lines of high intensity at 10.7, 16.6
and 17.4; lines of medium intensity at 5.8, 8.0, 8.9, 10.0, 10.1, 10.7,
15.7, 16.2 and 18.2; lines of weak intensity at 6.3, 6.5, 7.2, 11.6, 12.7,
13.6, 14.2, 14.9, 17.0, 18.7 and 19.6; and a relative configuration of the
three dibenzo d,f! 1.3.2!dioxaphosphepin rings of R*, R*, R*.
2. A composition stabilized against thermal, oxidative and actinic induced
degradation which comprises
(a) an organic material subject to thermal, oxidative or actinic induced
degradation, and
(b) an effective stabilizing amount of the alpha, monoclinic crystalline
form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite!, characterized by melting in the range of
145.degree.-165.degree. C. and by an X-ray diffraction pattern exhibiting
lines of very high intensity at 5.2; lines of high intensity at 10.7, 16.6
and 17.4; lines of medium intensity at 5.8, 8.0, 8.9, 10.0, 10.1, 10.7,
15.7, 16.2 and 18.2; lines of weak intensity at 6.3, 6.5, 7.2, 11.6, 12.7,
13.6, 14.2, 14.9, 17.0, 18.7 and 19.6; and a relative configuration of the
three dibenzo d,f! 1.3.2!dioxaphosphepin rings of R*, R*, R*.
3. A composition according to claim 2 wherein the organic material is a
natural, semi-synthetic or synthetic polymer.
4. A composition according to claim 3 wherein the polymer is a
thermoplastic polymer.
5. A composition according to claim 4 wherein the polymer is a polyolefin.
6. A composition according to claim 5 wherein the polyolefin is
polyethylene or polypropylene.
7. A composition according to claim 6 wherein the polyolefin is
polypropylene.
8. A composition according to claim 2 which additionally contains a
phenolic antioxidant, a light stabilizer or a processing stabilizer.
9. A composition according to claim 2 which additionally contains as a
coadditive at least one compound of the benzofuran-2-one type.
10. A composition according to claim 2 wherein component (a) is a
lubricant, lubricating oil, natural fat or wax, or fat or wax based on a
synthetic ester.
11. A process for stabilizing an organic material against oxidative,
thermal or actinic-induced degradation, which comprises
incorporating therein or applying thereto the alpha, monoclinic crystalline
form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite! according to claim 1.
Description
This invention pertains to a novel alpha crystalline modification of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl) phosphite!, to a process for preparing said modification, and to
compositions stabilized therewith.
BACKGROUND OF THE INVENTION
2,2',2"-Nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2
'-diyl)phosphite! is a compound having the formula I
##STR1##
This compound of formula I is useful as a processing stabilizer for organic
polymers as taught in U.S. Pat. Nos. 4,318,845 and 4,374,219. The compound
of formula I is disclosed as being a white powder melting at
121.degree.-134.degree. C. As such, the powdery product has defects in
terms of handling and apparent density, and exhibiting poor flowability,
diffusibility into polymers, meterability, storage stability and
hydrolytic stability.
It has now been found that the compound of formula I can be obtained in a
different crystalline modification as purified crystalline particles which
exhibit acceptable properties in respect to handling, apparent density,
flowability, meterability, storage stability and hydrolytic stability.
The new modification is characterized by a monoclinic crystalline form,
melting in the range of 145.degree.-165.degree. C. as given by the peak
temperature of the endotherm recorded by differential scanning calorimetry
(DSC); and by an X-ray diffraction pattern obtained using Cu--K.alpha.
which exhibits diffraction angles (2.THETA.) of relative intensity given
in the table below.
______________________________________
Diffraction Relative
Angle (2.THETA.)
Intensity (%)
______________________________________
5.2 100
5.8 38
6.3 13
6.5 15
7.2 14
8.0 30
8.7 31
8.9 36
10.0 35
10.1 31
10.7 41
11.6 18
12.7 7
13.6 20
14.2 23
14.9 18
15.7 30
16.2 31
16.6 48
17.0 28
17.4 58
18.2 37
18.7 20
19.6 20
20.0 17
20.2 17
20.8 17
21.1 18
22.6 18
22.7 18
22.9 18
23.1 16
______________________________________
The X-ray diffraction pattern thus shows angles (2.THETA.) lines of very
high intensity at 5.2; lines of high intensity at 10.7, 16.6 and 17.4;
lines of medium intensity at 5.8, 8.0, 8.9, 10.0, 10.1, 10.7, 15.7, 16.2
and 18.2; lines of weak intensity at 6.3, 6.5, 7.2, 11.6, 12.7, 13.6,
14.2, 14.9, 17.0, 18.7 and 19.6; and a relative absolute configuration of
the three stereo axes of the dibenzo d,f! 1,3,2!dioxaphosphepin rings of
R*,R*,R*.
R* follows the customary convention when the absolute configuration of a
molecule is unknown. The nomenclature adopted here is based on recent
Chemical Abstracts Service practice as described by L. C. Cross and W.
Kylne, Pure Appl. Chem. 45, 11-30 (1976).
The instant invention also relates to processes for the preparation of this
novel alpha crystalline modification of the compound of formula I.
The instant invention also pertains to a composition stabilized against
thermal, oxidative and actinic induced degradation which comprises
(a) an organic material subject to thermal, oxidative or actinic induced
degradation, and
(b) an effective stabilizing amount of the alpha, monoclinic crystalline
form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite! characterized by melting in the range of
145.degree.-165.degree. C. and by an X-ray diffraction pattern exhibiting
lines of very high intensity at 5.2; lines of high intensity at 10.7, 16.6
and 17.4; lines of medium intensity at 5.8, 8.0, 8.9, 10.0, 10.1, 10.7,
15.7, 16.2 and 18.2; lines of weak intensity at 6.3, 6.5, 7.2, 11.6, 12.7,
13.6, 14.2, 14.9, 17.0, 18.7 and 19.6; and a relative configuration of the
three dibenzo d,f! 1.3.2!dioxaphosphepin rings of R*, R*, R*.
The organic material is preferably a polymer processed at elevated
temperatures. Particularly preferred organic polymers are the polyolefins,
especially polypropylene and polyethylene, and polyamides. Most
particularly the organic polymer is polypropylene.
The compounds of this invention are very effective processing stabilizers
for polyolefins than the prior art compounds both in preventing molecular
weight changes as well as preventing discoloration.
In general polymers which can be stabilized include
1. Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or
polybutadiene, as well as polymers of cycloolefins, for instance of
cyclopentene or norbornene, polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE), low density
polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low
density polyethylene (BLDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding
paragraph, preferably polyethylene and polypropylene, can be prepared by
different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated
temperature).
b) catalytic polymerisation using a catalyst that normally contains one or
more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
These metals usually have one or more than one ligand, typically oxides,
halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or
aryls that may be either .pi.- or .sigma.-coordinated. These metal
complexes may be in the free form or fixed on substrates, typically on
activated magnesium chloride, titanium(III) chloride, alumina or silicon
oxide. These catalysts may be soluble or insoluble in the polymerisation
medium. The catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal hydrides,
metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals
being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The
activators may be modified conveniently with further ester, ether, amine
or silyl ether groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or
single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of
polypropylene with polyisobutylene, polypropylene with polyethylene (for
example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene
(for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other
vinyl monomers, for example ethylene/propylene copolymers, linear low
density polyethylene (LLDPE) and mixtures thereof with low density
polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene
copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers,
ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene copolymers, propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers,
ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers
and their copolymers with carbon monoxide or ethylene/acrylic acid
copolymers and their salts (ionomers) as well as terpolymers of ethylene
with propylene and a diene such as hexadiene, dicyclopentadiene or
ethylidene-norbornene; and mixtures of such copolymers with one another
and with polymers mentioned in 1) above, for example
polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate
copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA,
LLDPE/EAA and alternating or random polyalkylene/carbon monoxide
copolymers and mixtures thereof with other polymers, for example
polyamides.
4. Hydrocarbon resins (for example C.sub.5 -C.sub.9) including hydrogenated
modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and
starch.
5. Polystyrene, poly(p-methylstyrene), poly(.alpha.-methylstyrene).
6. Copolymers of styrene or .alpha.-methylstyrene with dienes or acrylic
derivatives, for example styrene/butadiene, styrene/acrylonitrile,
styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,
styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of
styrene copolymers and another polymer, for example a polyacrylate, a
diene polymer or an ethylene/propylene/diene terpolymer; and block
copolymers of styrene such as styrene/butadiene/styrene,
styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or .alpha.-methylstyrene, for example
styrene on polybutadiene, styrene on polybutadiene-styrene or
polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or
methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl
methacrylate on polybutadiene; styrene and maleic anhydride on
polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on
polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl
acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on
ethylene/propylene/diene terpolymers; styrene and acrylonitrile on
polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile
on acrylate/butadiene copolymers, as well as mixtures thereof with the
copolymers listed under 6), for example the copolymer mixtures known as
ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated
rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of
ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for example
polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,
polyvinylidene fluoride, as well as copolymers thereof such as vinyl
chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene
chloride/vinyl acetate copolymers.
9. Polymers derived from .alpha.,.beta.-unsaturated acids and derivatives
thereof such as polyacrylates and polymethacrylates; polymethyl
methacrylates, polyacrylamides and polyacrylonitriles, impact-modified
with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with
other unsaturated monomers, for example acrylonitrile/butadiene
copolymers, acrylonitrile/alkyl acrylate copolymers,
acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide
copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl
derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl
acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,
polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as
their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene
glycols, polyethylene oxide, polypropylene oxide or copolymers thereof
with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which
contain ethylene oxide as a comonomer, polyacetals modified with
thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides
with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters
or polybutadienes on the one hand and aliphatic or aromatic
polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic
acids and/or from aminocarboxylic acids or the corresponding lactams, for
example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,
12/12, polyamide 11, polyamide 12, aromatic polyamides starting from
m-xylene diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic or/and terephthalic acid and with or
without an elastomer as modifier, for example
poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene
isophthalamide; and also block copolymers of the aforementioned polyamides
with polyolefins, olefin copolymers, ionomers or chemically bonded or
grafted elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as polyamides
or copolyamides modified with EPDM or ABS; and polyamides condensed during
processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from
hydroxycarboxylic acids or the corresponding lactones, for example
polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as
well as block copolyether esters derived from hydroxyl-terminated
polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones. 21. Crosslinked
polymers derived from aldehydes on the one hand and phenols, ureas and
melamines on the other hand, such as phenol/formaldehyde resins,
urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and
unsaturated dicarboxylic acids with polyhydric alcohols and vinyl
compounds as crosslinking agents, and also halogen-containing
modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for
example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with
melamine resins, urea resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from polyepoxides, for example from
bisglycidyl ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically
modified homologous derivatives thereof, for example cellulose acetates,
cellulose propionates and cellulose butyrates, or the cellulose ethers
such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example
PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,
PBTP/ABS, PC/ASA PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,
PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and
copolymers, PA/HDPE, PA/PP, PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure
monomeric compounds or mixtures of such compounds, for example mineral
oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes
based on synthetic esters (e.g. phthalates, adipates, phosphates or
trimellitates) and also mixtures of synthetic esters with mineral oils in
any weight ratios, typically those used as spinning compositions, as well
as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or
latices of carboxylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,
for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes
described, for example, in U.S. Pat. No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate
resins or with unsaturated acrylic resins. The unsaturated acrylic resins
include the urethane acrylates, polyether acrylates, vinyl or acryl
copolymers with pendant unsaturated groups and the acrylated melamines.
The polyketimines are prepared from polyamines and ketones in the presence
of an acid catalyst.
33. Radiation curable compositions containing ethylenically unsaturated
monomers or oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by
an epoxy functional coetherified high solids melamine resin such as
LSE-4103 (Monsanto).
In general, the compounds of the present invention are employed in from
about 0.01 to about 5% by weight of the stabilized composition, although
this will vary with the particular substrate and application. An
advantageous range is from about 0.05 to about 3%, and especially 0.05 to
about 1%.
The stabilizers of the instant invention may readily be incorporated into
the organic polymers by conventional techniques, at any convenient stage
prior to the manufacture of shaped articles therefrom. For example, the
stabilizer may be mixed with the polymer in dry powder form, or a
suspension or emulsion of the stabilizer may be mixed with a solution,
suspension, or emulsion of the polymer. The resulting stabilized polymer
compositions of the invention may optionally also contain from about 0.01
to about 5%, preferably from about 0.025 to about 2%, and especially from
about 0.1 to about 1% by weight of various conventional additives, such as
the materials listed below, or mixtures thereof.
1. Antioxidants
1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol
2-tert-butyl-4,6-dimethylphenol
2,6-di-tert-butyl-4-ethylphenol
2,6-di-tert-butyl-4-n-butylphenol
2,6-di-tert-butyl-4-i-butylphenol
2,6-di-cyclopentyl-4-methylphenol
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol
2,6-di-octadecyl-4-methylphenol
2,4,6-tri-cyclohexylphenol
2,6-di-tert-butyl-4-methoxymethylphenol
1.2. Alkylated hydroquiones, for example,
2,6-di-tert-butyl-4-methoxyphenol
2,5-di-tert-butyl-hydroquinone
2,5-di-tert-amyl-hydroquinone
2,6-diphenyl-4-octadecyloxyphenol
1.3. Hydroxylated thiodiphenyl ethers, for example,
2,2'-thio-bis-(6-tert-butyl-4-methylphenol)
2,2'-thio-bis-(4-octylphenol)
4,4'-thio-bis-(6- tert-butyl-3-methylphenol)
4,4'-thio-bis-(6-tert-butyl-2-methylphenol)
1.4. Alkylidene-bisphenols, for example,
2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)
2,2'-methylene-bis- 4-methyl-6-(.alpha.-methylcyclohexyl)-phenol!
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)
2,2'-methylene-bis-(6-nonyl-4-methylphenol)
2,2'-methylene-bis- 6-(.alpha.-methylbenzyl)-4-nonylphenol!
2,2'-methylene-bis- 6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol!
2,2'-methylene-bis-(4,6-di-tert-butylphenol)
2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)
4,4'-methylene-bis-(2,6-di-tert-butylphenol)
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane
ethyleneglycol bis- 3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate!
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene
di- 2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphen
yl!terephthalate.
1.5. Benzyl compounds, for example,
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene
di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,
calcium-salt
1.6. Acylaminophenols, for example,
4-hydroxy-lauric acid anilide
4-hydroxy-stearic acid anilide
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine
octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate
1.7. Esters of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid
with monohydric or polyhydric alcohols, for example,
______________________________________
methanol diethylene glycol
octadecanol triethylene glycol
1,6-hexanediol pentaerythritol
neopentyl glycol
tris-hydroxyethyl isocyanurate
thiodiethylene glycol
di-hydroxyethyl oxalic acid diamide
______________________________________
1.8. Esters of .beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic
acid with monohydric or polyhydric alcohols, for example,
______________________________________
methanol diethylene glycol
octadecanol triethylene glycol
1,6-hexanediol pentaerythritol
neopentyl glycol
tris-hydroxyethyl isocyanurate
thiodiethylene glycol
di-hydroxyethyl oxalic acid diamide
______________________________________
1.9. Amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid
for example,
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine
N,N'-di-(3,5-di- tert-butyl-4-hydroxyphenylpropionyl)-hydrazine
1.10 Diarylamines, for example, diphenylamine, N-phenyl-1-naphthylamine,
N-(4-tert-octylphenyl)-1-naphthylamine, 4,4'-di-tert-octyl-diphenylamine,
reaction product of N-phenylbenzylamine and 2,4,4-trimethylpentene,
reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction
product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.
2. UV absorbers and light stabilizers
2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,
3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,
5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,
3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-,
3',5'-bis-.alpha.,.alpha.-dimethylbenzyl),
3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl-,
3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,
and dodecylated-5'-methyl derivatives.
2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,
4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy- and
2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of optionally substituted benzoic acids for example, phenyl
salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,
dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,
benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid
2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid
hexadecyl ester.
2.4. Acrylates, for example, .alpha.-cyano-.beta.,.beta.-diphenylacrylic
acid ethyl ester or isooctyl ester, .alpha.-carbomethoxy-cinnamic acid
methyl ester, .alpha.-cyano-.beta.-methyl-p-methoxy-cinnamic acid methyl
ester or butyl ester, .alpha.-carbomethoxy-p-methoxy-cinnamic acid methyl
ester, N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methyl-indoline.
2.5. Nickel compounds, for example, nickel complexes of
2,2'-thio-bis- 4-(1,1,3,3-tetramethylbutyl)-phenol!, such as the 1:1 or
1:2 complex, optionally with additional ligands such as n-butylamine,
triethanolamine or N-cyclohexyl-diethanolamine, nickel
dibutyldithiocarbamate, nickel salts of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as
of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as
of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of
1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. Sterically hindered amines, for example
bis-(2,2,6,6-tetramethylpiperidyl)sebacate,
bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate,
n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid
bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid,
condensation product of
N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-s-triazine,
tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.
2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,
2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,
2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,
2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and
para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
2.8. Hydroxyphenyl-s-triazines, for example
2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;
2,4-bis 2-hydroxy-4-(2-hydroxyethoxy-phenyl!-6-(4-chlorophenyl)-s-triazine
; 2,4-bis 2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl!-6-(2,4-dimethyl
phenyl)-s-triazine;
2,4-bis 2-hydroxy-4-(2-hydroxyethoxy)phenyl!-6-(4-bromophenyl)-s-triazine;
2,4-bis 2-hydroxy-4-(2-acetoxyethoxy)phenyl!-6-(4-chlorophenyl)-s-triazine
, 2,4-bis (2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.
3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,
N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,
N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,
3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.
4. Phosphites and phosphonites, for example, triphenyl phosphite,
diphenylalkyl phosphites, phenyldialkyl phosphites,
tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,
di-stearyl-pentaerythritol diphosphite,
tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol
diphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,
tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)
4,4'-diphenylylenediphosphonite.
5. Compounds which destroy peroxide, for example, esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl, myristyl or
tridecyl esters, mercapto-benzimidazole or the zinc salt of
2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl
disulfide, pentaerythritol tetrakis-(.beta.-dodecylmercapto)-propionate.
6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived
from hydrogenated tallow amine.
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,
N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,
N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,
N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone,
N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl
nitrone, N-heptadecyl-alpha-heptadecyl nitrone,
N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
8. Polyamide stabilizers, for example copper salts in combination with
iodides and/or phosphorus compounds and salts of divalent manganese.
9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,
dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine
derivatives, amines, polyamides, polyurethanes, alkali metal salts and
alkaline earth metal salts of higher fatty acids for example Ca stearate,
Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony
pyrocatecholate or zinc pyrocatecholate.
10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid,
diphenylacetic acid.
11. Fillers and reinforcing agents, for example, calcium carbonate,
silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,
metal oxides and hydroxides, carbon black, graphite.
12. Other additives, for example, plasticizers, lubricants, emulsifiers,
pigments, optical brighteners, flameproofing agents, anti-static agents,
blowing agents and thiosynergists such as dilauryl thiodipropionate or
distearyl thiodipropionate.
13. Benzofuranones and indolinones, for example those disclosed in U.S.
Pat. Nos. 4,325,863, 4,338,244 or 5,175,312, or
3- 4-(2-acetoxyethoxy)phenyl!-5,7-di-tert-butyl-benzofuran-2-one,
5,7-di-tert-butyl-3- 4-(2-stearoyloxyethoxy)phenyl!benzofuran-2-one,
3,3'-bis 5,7-di-tert-butyl-3-(4- 2-hydroxyethoxy!phenyl)benzofuran-2-one!,
5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The co-stabilizers, with the exception of the benzofuranones listed under
11, are added for example in concentrations of 0.01 to 10%, relative to
the total weight of the material to be stabilized.
Further preferred compositions comprise, in addition to components (a) and
(b) further additives, in particular phenolic antioxidants, light
stabilizers or processing stabilizers.
Particularly preferred additives are phenolic antioxidants (item 1 of the
list), sterically hindered amines (item 2.6 of the list), phosphites and
phosphonites (item 4 of the list) and peroxide-destroying compounds (item
5.) of the list.
Additional additives (stabilizers) which are also particularly preferred
are benzofuran-2-ones, such as described, for example, in U.S. Pat. Nos. 4
325 863, 4,338 244 or 5,175,312.
Examples of such benzofuran-2-ones are compounds of the formula
##STR2##
in which R.sub.11 is phenyl or phenyl which is substituted by 1 to 3 alkyl
radicals together having at most 18 carbon atoms, alkoxy having 1 to 12
carbon atoms, alkoxycarbonyl having 2 to 18 carbon atoms or chlorine;
R.sub.12 is hydrogen;
R.sub.14 is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl,
cyclohexyl or chlorine;
R.sub.13 has the meaning of R.sub.12 or R.sub.14 or is a radical of the
formula
##STR3##
in which R.sub.16 is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl
having 2 to 18 carbon atoms which is interrupted by oxygen or sulfur,
dialkylaminoalkanol having a total of 3 to 16 carbon atoms, cyclopentyl,
cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals
together having at most 18 carbon atoms;
n is 0, 1 or 2;
the substituents R.sub.17, independently of one another, are hydrogen,
alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl
which is substituted by 1 or 2 alkyl radicals together having at most 16
carbon atoms, a radical of the formula
##STR4##
or together with the nitrogen atom to which they are attached form a
piperidine or morpholine radical;
m is 1 to 18;
R.sub.20 is hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl
having 5 to 12 carbon atoms;
A is alkylene having 2 to 22 carbon atoms which may be interrupted by
nitrogen, oxygen or sulfur;
R.sub.8 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl,
cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals
together having at most 16 carbon atoms, or is benzyl;
R.sub.19 is alkyl having 1 to 18 carbon atoms;
D is --O--, --S--, --SO--, --SO.sub.2 -- or --C(R.sub.21).sub.2 --;
the substituents R.sub.21, independently of one another, are hydrogen,
C.sub.1 -C.sub.6 alkyl, the two R.sub.21 together containing 1 to 16
carbon atoms, R.sub.21 is furthermore phenyl or a radical of the formula
##STR5##
in which n, R.sub.16 and R.sub.17 are as defined above; E is a radical of
the formula
##STR6##
in which R.sub.11, R.sub.12 and R.sub.14 are as defined above; and
R.sub.15 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl,
cyclohexyl, chlorine or a radical of the formula
##STR7##
in which R.sub.16 and R.sub.17 are as defined above, or R.sub.15 together
with R.sub.14 forms a tetramethylene radical.
Preference is given to those benzofuran-2-ones in which R.sub.13 is
hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl,
chlorine or a radical of the formula
##STR8##
or --D--E, in which n, R.sub.16, R.sub.17, D and E are as defined above,
R.sub.16 is in particular hydrogen, alkyl having 1 to 18 carbon atoms,
cyclopentyl or cyclohexyl.
Preference is given furthermore to those benzofuran-2-ones in which
R.sub.11 is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals
together having at most 12 carbon atoms; R.sub.12 is hydrogen; R.sub.14 is
hydrogen or alkyl having 1 to 12 carbon atoms; R.sub.13 is hydrogen, alkyl
having 1 to 12 carbon atoms,
##STR9##
or --D--E; R.sub.5 is hydrogen, alkyl having 1 to 20 carbon atoms
##STR10##
or R.sub.15 together with R.sub.14 forms a tetramethylene radical, n,
R.sub.16, R.sub.17, D and E being as defined at the beginning.
Of particular interest are aim those benzofuran-2-ones in which R.sub.11 is
phenyl; R.sub.13 is hydrogen, alkyl having 1 to 12 carbon atoms or --D--E;
R.sub.12 and R.sub.14, independently of one another, are hydrogen or alkyl
having 1 to 4 carbon atoms; and R.sub.15 is alkyl having 1 to 20 carbon
atoms, D and E being as defined at the beginning.
Of special interest are finally also those benzofuran-2-ones in which
R.sub.11 is phenyl; R.sub.13 is alkyl having 1 to 4 carbon atoms or
--D--E; R.sub.12 and R.sub.14 are hydrogen; and R.sub.15 is alkyl having 1
to 4 carbon atoms, cyclopentyl or cyclohexyl, D being a group
--C(R.sub.21).sub.2 -- and E being a radical of the formula
##STR11##
the substituents R.sub.21 being identical to or different from one another
and each being alkyl having 1 to 4 carbon atoms, and R.sub.11, R.sub.12,
R.sub.14 and R.sub.15 being as defined.
The amount of additional additives, in particular stabilizers, for example
of the benzofuran-2-ones mentioned, can vary within wide limits. For
example, 0.0005 to 10, preferably 0.001 to 5, in particular 0.01 to 2, %
by weight thereof can be present in the compositions according to the
invention.
Incorporation of the alpha, monoclinic crystalline form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite! and, if desired, further additives in the polymer
organic material is carried out by known methods, for example before or
during moulding or by applying the dissolved or dispersed compounds to the
polymer organic material, if appropriate with subsequent slow evaporation
of the solvent. The alpha, monoclinic modification according to the
invention can also be added to the materials to be stabilized in the form
of a masterbatch containing them, for example, in a concentration of 2.5
to 25% by weight.
The alpha, monoclinic modification according to the invention can also be
added before or during polymerization or before crosslinking.
The alpha, monoclinic modification according to the invention can be
incorporated in the material to be stabilized in pure form or encapsulated
in waxes, oils or polymers.
The alpha, monoclinic modification according to the invention can also be
sprayed onto the polymer to be stabilized. They are capable of diluting
other additives (for example the abovementioned customary additives) or
their melts, thus enabling them to be sprayed onto the polymer to be
stabilized also together with these additives. Addition by spraying during
deactivation of the polymerization catalysts is particularly advantageous,
it being possible, for example, for the steam used for deactivation to be
used for spraying.
In the case of bead polymerized polyolefins, it may be advantageous, for
example, to apply the alpha, monoclinic modification according to the
invention, if desired together with other additives, by spraying.
The materials thus stabilized can be used in a wide range of forms, for
example as films, fibres, tapes, moulding compositions, profiles or as
binders for paints, adhesives or cements.
As already mentioned, the organic materials to be protected are preferably
organic, in particular synthetic, polymers. Of these, the materials being
protected are particularly advantageously thermoplastic materials, in
particular polyolefins. The excellent efficiency of the alpha, monoclinic
form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite! as processing stabilizer (thermal stabilizer) should be
mentioned in particular. To this end, it is advantageously added to the
polymer before or during its processing. It is however also possible to
stabilize other polymers (for example elastomers) or lubricants or
hydraulic fluids against degradation, for example light-induced or
thermal-oxidative degradation. For elastomers, see the above list of
possible organic materials.
Suitable lubricants and hydraulic fluids are based, for example, on mineral
or synthetic oils or mixtures thereof. Lubricants are known to one skilled
in the art and described in the relevant technical literature, for example
in Dieter Klamann, "Schmierstoffe und verwandte Produkte" (Verlag Chemic,
Weinheim 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" (Dr.
Alfred Huthig-Verlag, Heidelberg, 1974) and in "Ullmanns Enzyklopadie der
technischen Chemic" vol. 13, pages 85-94 (Verlag Chemic, Weinheim, 1977).
Accordingly, a preferred embodiment of the present invention is the process
of using the alpha, monoclinic form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite! for stabilizing organic materials against oxidative,
thermal or light-induced degradation.
The alpha, monoclinic modification according to the invention is preferably
used as processing stabilizer (thermal stabilizer) of thermoplastic
polymers.
The present invention also provides a process for stabilizing an organic
material against oxidative, thermal or light-induced degradation, which
comprises incorporating therein or applying thereto the alpha, monoclinic
form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite!.
The phenolic antioxidant of particular interest is selected from the group
consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),
di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),
2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol),
1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,
1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
1,3,5-tris 2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl!isocyanur
ate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),
1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,
N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),
calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene
bis 3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate!, octyl
3,5-di-tert-butyl-4-benzylmercaptoacetate,
bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and
N,N'-bis 2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl!-oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl
3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
2,6-di-tert-butyl-p-cresol or
2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
The hindered amine compound of particular interest is selected from the
group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,
di(1,2,2,6,6-pentamethylpiperidin-4-yl)
(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro 4.5!decane-2,4-dione,
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,
1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro 5.1.11.2!heneicosane,
polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
polycondensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic
acid, polycondensation product of
4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and
1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)
1,2,3,4-butanetetracarboxylate,
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)
1,2,3,4-butanetetracarboxylate, polycondensation product of
2,4-dichloro-6-morpholino-s-triazine and
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
N,N',N",N"'-tetrakis (4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-am
ino-s-triazin-2-yl!-1,10-diamino-4,7-diazadecane, mixed
2,2,6,6-tetramethylpiperidin-4-yl/.beta.,.beta.,.beta.',.beta.'-tetrameth
yl-3,9-(2,4,8,10-tetraoxaspiro 5.5!undecane)diethyl!1,2,3,4-butanetetracarb
oxylate, mixed
1,2,2,6,6-pentamethylpiperidin-4-yl/.beta.,.beta.,.beta.',.beta.'-tetrame
thyl-3,9-(2,4,8,10-tetraoxaspiro 5.5!undecane)diethyl!1,2,3,4-butanetetraca
rboxylate, octamethylene bis(2,2,6,6-tetra-methylpiperidin-4-carboxylate),
4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), and
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.
A most preferred hindered amine compound is
bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, the polycondensation
product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl4-hydroxypiperdine and
succinic acid, the polycondensation product of
2,4-dichloro-6-tert-octylamino-s-triazine and
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
N,N',N",N"'-tetrakis (4,6-bis(butyl-1-(2,2,6,6-tetramethyl-piperidin-4-yl)
amino )-s-triazine-2-yl!-1,10-diamino-4,7-diazadecane or
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.
The lubricating oil may be a mineral oil, a synthetic oil or any mixture of
such oils. Mineral oils are preferred and examples of these include
paraffinic hydrocarbon oils e.g. a mineral oil having a viscosity of 46
mm.sup.2 /s at 40.degree. C.; "150 Solvent Neutral" a solvent refined
neutral mineral oil having a viscosity of 32 mm.sup.2 /s at 40.degree. C.;
and "solvent bright-stocks", a high boiling residue from the process of
refining mineral oil, and having a viscosity of 46 mm.sup.2 /s at
40.degree. C.
Synthetic lubricating oils which may be present may be synthetic
hydrocarbons such as polybutenes, alkyl benzenes and poly-alpha olefins as
well as simple di-, tri- and tetra-esters, complex esters and polyesters
derived from carboxylic acid esters of formula: G.sub.1
--OCC-alkylene-COOG.sub.2 wherein "alkylene" denotes an alkylene residue
having from 2 to 14 carbon atoms and G.sub.1 and G.sub.2 are the same or
different and each is an alkyl group having from 6 to 18 carbon atoms.
Tri-esters which are of use as lubricating oil base stocks are those
derived from trimethylolpropane and C.sub.6 -C.sub.18 mono-carboxylic
acids or mixtures thereof, whereas suitable tetra-esters include those
derived from pentaerythritol and a C.sub.6 -C.sub.18 mono-carboxylic acid
or mixtures thereof.
Complex esters suitable for use as components of the composition of the
present invention are those derived from monobasic acids, dibasic acids
and polyhydric alcohols, for instance the complex ester derived from
trimethylol propane, caprylic acid and sebacic acid.
Suitable polyesters are those derived from any aliphatic dicarboxylic acid
having from 4 to 14 carbon atoms and at least one aliphatic dihydric
alcohol having from 3 to 12 carbon atoms, e.g. those derived from azelaic
acid or sebacic acid and 2,2,4-trimethylhexane-1,6-diol.
Other lubricating oils are those known to the m-skilled and described e.g.
in Schewe-Kobek, "Schmiermittel-Taschenbuch", (Huethig Verlag, Heidelberg
1974), and in D. Klamann, "Schmierstoff und verwandte Produkte", (Verlag
Chemie, Weinheim 1982).
The lubricating oils applicational media can aim contain other additives
which may be added to improve the basic properties of lubricants e.g.
metal passivators, viscosity-index improvers, pour-point depressants,
dispersing agents, detergents, additional rest inhibitors, extreme
pressure additives, anti-wear additives and antioxidants.
Examples of phenolic antioxidants
1. Alkylated Monophenols 2,6-Di-tert-butyl-4-methylphenol,
2,6-di-tert-butylphenol,
2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethyl-phenol,
2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol,
2,6-di-cyclopentyl-4-methylphenol,
2-(.beta.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-di-octa-decyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol.
2. Alkylated Hydroquinones 2,6-Di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone,
2,6-diphenyl-4-octa-decyloxyphenol.
3. Hydroxylated Thiodiphenylethers
2,2'-Thio-bis-(6-tert-butyl-4-methylphenol),
2,2'-thio-bis-(4-octyl-phenyl),
4,4'-thio-bis-(6-tert-butyl-3-methylphenol),
4,4'-thio-bis-(6-tert-butyl-2-methylphenol).
4. Alkylidene-Bisphenols 2,2'-Methylene-bis-(6-tert-butyl-4-methylphenol),
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol),
2,2'-methylene-bis-(4-methyl-6-(.alpha.-methyl -cyclohexyl)-phenol),
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol),
2,2'-methylene-bis-(6-nonyl-4-methylphenol),
2,2'-methylene-bis-(4,6-di-tert-butylphenol),
2,2'-ethylidene-bis-(4,6-di-tert-butylphenol),
2,2'-ethylidene-bis-(6-tert-butyl-4- or -5-isobutylphenol),
2,2'-methylene-bis-(6-(.alpha.-methylbenzyl-4-nonylphenol),
2,2'-methylene-bis-(6-(.alpha.,.alpha.-di-methylbenzyl)-4-nonylphenol),
4,4'-methylene-bis-(2,6-di-tert-butyl-phenol),
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol),
1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl-phenol)-butane,
2,6-di-(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methyl-phenol,
1,1,3-tris-(5-tert-butyl
-4-hydroxy-2-methylphenyl)-3-n-dodecyl)-mercaptobutane,
ethyleneglycol-bis- 3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate !,
bis-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene,
bis- 2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methyl-p
henyl!-terephthalate.
5. Benzyl Compounds
1,3,5-Tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene,
bis(3,5-di-tert-butyl-4-hydroxybenzyl)-sulfide,
3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid-isooctylester,
bis-(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithiolterephthalate,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate,
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate,
3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-dioctadecylester,
3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-monoethylester,
calcium-salt.
6. Acylaminophenols 4-Hydroxy-lauric acid anilide, 4-hydroxy-stearic acid
anilide,
2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine,
N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester.
7. Esters of .beta.-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionic acid with
mono- or polyhydric alcohols, for example with methanol, isooctyl alcohol,
2-ethylhexanol, diethylene glycol, octadecanol, triethylene glycol,
1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-hydroxyethyl
isocyanurate, thiodiethylene glycol, bis-hydroxyethyl-oxalic acid diamide.
8. Esters of .beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid
with mono- or polyhydric alcohols, for example with methanol, isooctyl
alcohol, 2-ethylhexanol, diethylene glycol, octadecanol, triethylene
glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol,
tris-hydroxyethyl isocyanurate,thiodiethylene glycol,
di-hydroxyethyl-oxalic acid diamide.
9. Amides of .beta.-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionic acid for
example
N,N'-Bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylene-diamin
e,
N,N'-bis-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-trimethylene-diamin
e, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
Examples of amine antioxidants:
N,N'-Di-isopropyl-p-phenylenediamine,
N,N'-di-sec.-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phe
nylenediamine, N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine,
N,N'-bis(1-methyl-heptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,
N,N'-di-(naphthyl-2-)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methyl-heptyl)-N'-phenyl-p-phenylene-diamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluene-sulfonamido)-diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, di-phenylamine,
N-allyldiphenylamine, 4-isopropoxy-diphenylamine,
N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated
diphenylamine, e.g. p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylamino-phenol, 4-nonanoylamino-phenol, 4-dodecanoyl-amino-phenol,
4-octadecanoyl-amino-phenol, di-(4-methoxy-phenyl)-amine,
2,6-di-tert-butyl-4-dimethyl-amino-methyl-phenol,
2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenyl-methane,
N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane,
1,2-di-(phenyl-amino)-ethane, 1,2-di- 2-methyl-phenyl)-amino!-ethane,
1,3-di-(phenylamino)-propane, (o-tolyl)-biguanide,
di- 4-1',3'-dimethyl-butyl)-phenyl!amine, tert-octylated
N-phenyl-1-naphthylamine, mixture of mono- and dialkylated
tert-butyl-/tert-octyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
N-allylphenothiazine, tert-octylated phenothiazine,
3,7-di-tert-octylphenothiazine.
Examples for other antioxidants:
Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of
thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid.
Examples of metal passivators, for example for copper, are:
Triazoles, benzotriazoles and derivatives thereof, tolutriazole and
derivatives thereof, e.g. di(2-ethylhexyl)-aminomethyltolutriazole,
2-mercaptobenzothiazole, 5,5'-methylene-bis-benzotriazole,
4,5,6,7-tetrahydrobenzo-triazole, salicyclidene-propylene-diamine and
salicyclamino-guanidine and salts thereof, 1,2,4-triazole and
N,N'-disubstituted aminomethyl triazoles of formula
##STR12##
in which R.sub.8 and R.sub.9 are, independently, e.g. alkyl, alkenyl, or
hydroxyethyl, obtained by reacting 1,2,4-triazole with formaldehyde and an
amine, HNR.sub.8 R.sub.9, as disclosed in European Patent Application No.
160620; and the Mannich reaction products derived from benzotriazole or
tolutriazole, formaldehyde and an amine HNR.sub.8 R.sub.9.
Examples of rust inhibitors are:
a) Organic acids, their esters, metal salts and anhydrides, e.g.
N-oleoyl-sarcosine, sorbitan-mono-oleate, lead-naphthenate,
alkenyl-succinic acids and -anhydrides, e.g. dodecenyl-succinic acid
anhydride, succinic acid partial esters and amines, 4-nonyl-phenoxy-acetic
acid.
b) Nitrogen-containing compounds, e.g.
I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and
amine-salts of organic and inorganic acids, e.g. oil-soluble
alkyl-ammonium carboxylates
II. Heterocyclic compounds, e.g. substituted imidazolines and oxazolines.
c) Phosphorus-containing compounds, e.g. amine salts of phosphonic acid or
phosphoric acid partial esters, zinc dialkyldithio phosphates.
d) Sulfur-containing compounds, e.g.
barium-dinonylnaphthalene-n-sulfonates, calcium petroleum sulfonates.
e) Derivatives of gamma-alkoxypropylamines described in Japanese Patent
Publication No. 15783/1973; and
f) Salts having the formula Y--NH.sub.3 --R.sub.10 CO.sub.2 -- in which y
is a group R.sub.11 X.sub.1 CH.sub.2 CH(OH)CH .sub.2 in which R.sub.10 and
R.sub.11, independently, are e.g. alkyl and X1 is O, CO.sub.2, NH,
N(alkyl), N(alkenyl) or S, these salts being prepared by mixing an amine
Y--NH.sub.2 with an acid R.sub.10 CO.sub.2 H, as disclosed in DE-OS 3437
876 (German Offenlegungsschrift).
g) Compounds having the formula
R.sub.12 --X.sub.2 --CH.sub.2 --CH(OH)--CH.sub.2 NR.sub.13 R.sub.14
in which X.sub.2 is ---O--, --S--, --SO.sub.2 --C(O)--O-- or --N(Rd) in
which R.sub.12 is H or C.sub.1 -C.sub.12 alkyl, R.sub.13 is unsubstituted
C.sub.1 -C.sub.4 alkyl or C.sub.2 -C.sub.5 alkyl substituted by one to
three hydroxyl groups, R.sub.14 is hydrogen, unsubstituted C.sub.1
-C.sub.4 alkyl or C.sub.2 -C.sub.5 alkyl substituted by one to three
hydroxyl groups provided that at least one of R.sub.13 and R.sub.14 is
hydroxy-substituted, and R.sub.12 is C.sub.2 -C.sub.20 alkyl --CH.sub.2
--CH(OH)--CH.sub.2 NR.sub.13 R.sub.14 or R.sub.12 is C.sub.2 -C.sub.18
alkenyl, C.sub.2 -C.sub.3 alkynyl or C.sub.5 -C.sub.12 cycloalkyl provided
that, when X.sub.2 is ---O-- or --C(O)--O--, R.sub.12 is branched C.sub.4
-C.sub.20 alkyl. These compounds are described in GB Patent Specification
2172284A.
h) Compounds having the formula:
##STR13##
in which R.sub.15, R.sub.16, R.sub.17 are, independently, hydrogen,
C.sub.1 -C.sub.15 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.6 -C.sub.15
aryl or C.sub.7 -C.sub.12 aralkyl and R.sub.18 and R.sub.19,
independently, are hydrogen, 2-hydroxyethyl or 2-hydroxypropyl, provided
that R.sub.18 and R.sub.19 are not simultaneously hydrogen and, when
R.sub.18 and R.sub.19 are each --CH.sub.2 CH.sub.2 OH, R.sub.15 and
R.sub.16 are not simultaneously hydrogen and R.sub.17 is not pentyl. These
compounds are described in EP Patent specification 0 252 007.
Examples of viscosity-index improvers are:
Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate-copolymers,
polyvinylpyrrolidones, polybutanes, olefin-copolymers,
styrene/-acrylate-copolymers, polyethers.
Examples of pour-point depressants are:
Polymethacrylates, alkylated naphthalene derivatives.
Examples of dispersants/detergents are:
Polybutenylsuccinic acid-amides or -imides, polybutenyl-phosphonic acid
derivatives, basic magnesium-, calcium-, and bariumsulfonates and
-phenolates.
Examples of anti-wear additives and extreme pressure additives are:
Sulphur- and/or phosphorus- and/or halogen-containing compounds e.g.
sulphurised vegetable oils, zinc dialkyldithiophosphates,
tritolylphosphate, chlorinated paraffins, alkyl- and aryldi- and
trisulphides, triphenylphosphorothionate.
The instant alpha crystalline modification is obtained by a process of
crystallizing or recrystallizing the compound of formula I from a mixture
of an aromatic hydrocarbon solvent and an alcohol of 1 to 3 carbon atoms;
from an ether solvent; from an ester solvent; or from a mixture of a
halogenated aliphatic hydrocarbon solvent and a lower carbon chain
alcohol.
The preferred process for preparing the novel alpha crystalline
modification is by crystallizing or recrystallizing the compound of
formula I from a mixture of an aromatic hydrocarbon solvent and a lower
carbon chain alcohol.
A preferred embodiment of the instant process involves isolating the
crystalline mass from any of the above processes and drying it under
vacuum at elevated temperature.
Examples of aromatic hydrocarbon solvents useful in the instant process are
benzene, toluene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene,
1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene,
1,2,4,5-tetramethylbenzene, ethylbenzene, cumene, o-cymene, m-cymene,
p-cymene, o-diisopropylbenzene, m-diisopropylbenzene,
p-diisopropylbenzene, and mixtures of such aromatic hydrocarbon solvents.
Examples of lower carbon chain alcohols of 1 to 3 carbon atoms are
methanol, ethanol, 1-propanol, isopropanol and mixtures of such lower
alkanols.
Examples of ester solvents are methyl formate, ethyl formate, methyl
acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate
and the like.
Examples of ether solvents are diethyl ether, diisopropyl ether, methyl
tert-butyl ether and the like.
Examples of halogenated aliphatic hydrocarbon solvents are methylene
chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane and
the like.
Differential scanning calorimetry (DSC) measurements are obtained on a TA
Instrument Inc., 910 differential scanning calorimeter, with a 100 mL/min
nitrogen purge, aligned aluminum pan, temperature scan at 5.degree. C./min
to 230.degree. C.
X-ray diffraction patterns are recorded on a Philips Norelco X-ray
Dfffractometer unit, using Cu--K.alpha. radiation with a nickel filter.
EXAMPLE 1
The compound of formula I,
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite!, is prepared according to procedure of Example 4 of U.S.
Pat. No. 4,318,845. The product obtained is recrystallized from the
following solvent systems to obtain the novel alpha crystalline
modification of the instant invention.
______________________________________
Compound/
Solvent Ratio (%)
Solvent (wt/wt)
(wt/wt) mp (.degree.C.)*
Yield
______________________________________
ethyl acetate 1/3.8 160 74
toluene/ 1/7 158 75
isopropanol (1/6)
toluene/ 7/3 155 85
isopropanol (7/3)
xylene/ 1.2/1 159 91
isopropanol (1/1)
xylene/ 1.5/1 159 97
methanol (1.8/1)
toluene/ 1/2 159 91
methanol (1/1)
toluene/ 1/8.3 159 50
methanol (1.1/1)
diethyl ether 1/3.5 165 25
isopropanol/ 1/7.25 161 38
dichloromethane (1.2/1)
xylene/ 1.2/1 163 93
1-propanol (1/1)
______________________________________
*Melting point is determined by differential scanning calorimetry and the
peak temperature in the endotherm is recorded as the melting point.
Suitable crystals for X-ray analysis are grown from ethyl acetate. For the
structure determination, a thick hexagonal plate is selected and broken to
reduce the largest dimension to less than 1 mm. Intensity data are
measured on a Siemens R3MV four circle diffractometer as described in
Table 1 below. The structure is solved by direct methods using Siemens
SHELXTL PLUS (VMS). Full-matrix least-square refinements are carried out.
The relative absolute configuration is determined to be R*, R*, R*.
TABLE 1
______________________________________
Crystal and Data Collection Parameters
______________________________________
Formula C.sub.90 H.sub.132 NO.sub.9 P.sub.3
Formula weight (g .multidot. mol.sup.-1)
1464.96
Color; Habit Colorless Hexagonal Prism
Crystal System Monoclinic
Space group P2.sub.1 /n
Z 4
Cell parameters a = 20.0700 (10) .ANG.
b = 17.477 (2) .ANG.
c = 27.620 (3) .ANG.
.beta. = 93.050 (10) deg
Volume .nu. = 9674.5 (14) .ANG..sup.3
d.sub.calc 1.006
Absorption Coefficient
0.926 mm.sup.-1
Crystal Size 0.3 .times. 0.3 .times. 0.6 mm
F(000) 3184
Temperature 23 C.
Diffractometer Type
Siemens R3m/V
Radiation CuK.alpha.(.lambda. = 1.54178 .ANG.)
Monochromator Orientated graphite crystal
20 Range 3.15 to 115.0 deg
Scan Type 2.THETA.-.THETA.
Scan Range (w) 0.50.degree. plus K.alpha. separation
Reflections Collected
14042
No. of observed reflections
9094 (F > 3.0 .sigma. (F))
R 0.1159
R.sub.w 0.1690
______________________________________
EXAMPLE 2
Comparative Example
The compound of formula I, prepared according to the procedure of Example 4
of U.S. Pat. No. 4,318,845 and not recrystallized according to the
procedure of Example 1 of this application, is heated at 210.degree. C.
until a clear melt is obtained. The melt is cooled rapidly to ambient
temperature to yield a glassy solid with a T.sub.g (DSC) of
105.degree.-110.degree. C. The X-ray diffraction pattern of this product
obtained using Cu--K.alpha. is featureless.
Analysis: Calcd. for C.sub.90 H.sub.132 NO.sub.9 P.sub.3 : C, 73.8; H, 9.1;
N, 0.96. Found: C, 73.4; H, 9.3; N, 0.9.
EXAMPLE 3
Resistance to Hydrolysis
This example illustrates the much greater resistance to hydrolysis of the
alpha crystalline modification of the compound of formula I as prepared in
Example 1 as compared to the lesser resistance of the amorphous form of
the compound of formula I as prepared in Example 2.
The test compounds are exposed to 80% relative humidity at 50.degree. C.
and their rate of hydrolysis is monitored by liquid chromatography. The
results below are stated in the percent product remaining after 1000 hours
of exposure under the conditions stated above.
______________________________________
Percent Product
Remaining After
Compound of 1000 hours
______________________________________
Example 1 75
(alpha crystalline form)
Example 2 50
(amorphous)
______________________________________
This example illustrates the superior flowability properties of the new
alpha crystalline modification of the compound of formula I prepared in
Example 1 as compared to the flow properties of the compound of formula I
as prepared according to the procedure of Example 4 of U.S. Pat. No.
4,318,845.
The angle of repose is measured according to the procedure reported by G.
Gold et at. in J. Pharm. Sci., 55, 1291 (1966). A smaller angle of repose
indicated a superior flowing solid product.
______________________________________
Compound of Angle of Repose (degrees)
______________________________________
polypropylene control
38
Example 1 38
(alpha crystalline form)
Example 4 of U.S.
43
4,318,845 (prior art)
______________________________________
EXAMPLE 5
Process Stabilization of Propylene at 525.degree. F. (274.degree. C.)
The blank formulation comprises unstabilized polypropylene (PROFAX 6501,
Himont) containing 0.075% by weight of calcium stearate. The test
additives are incorporated into the polypropylene by dry blending or, when
the additive is a liquid, using a minimum mount of methylene chloride
solvent. The solvent is then removed by evaporation under reduced
pressure. The stabilized resin formulation is extruded at 90 rpm from a 1
inch (2.54 cm) diameter extruder at 525.degree. F. (274.degree. C.) with a
residence time of 90 seconds.
After each of the first, third and fifth extrusions, the melt flow rate (in
grams/10 minutes) is determined by ASTM method D1238 on the pellets
obtained from the extruder. The results are given in the table below.
______________________________________
Additive* Concentration
Melt Flow after Extrusion
Compound of (% by weight)
1 3 5
______________________________________
Blank -- 13.5 24.0 45.2
Base** 0.075 8.1 12.9 17.5
AO A plus 0.075
Compound of 0.075 6.3 6.6 7.5
Example 4 of
U.S. 4,318,845
AO A plus 0.075
Example 1 0.075 5.6 6.7 7.4
______________________________________
*Blank contains 0.075% by weight of calcium stearate.
**AO A is neopentanetetrayl
tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).
The instant alpha, monoclinic crystalline compound is particularly
effective in stabilizing polypropylene against thermal and oxidative
degradation as shown by a minimum change in the melt flow rate in the
presence of a representative phenolic antioxidant and is equal or more
effective that the prior art compound of U.S. Pat. No. 4,318,845.
Pellets obtained after the first, third and fifth extrusions are
compression molded into 125 mil (3.2 mm) plaques at 450.degree. F.
(232.degree. C.) and the yellowness index (YI) values are determined
according to ASTM method D1925. Lower YI values indicate less
discoloration. The results are given in the table below.
______________________________________
Yellowness Index (YI)
Additive* Concentration
Values after Extrusion
Compound of (% by weight)
1 3 5
______________________________________
Blank -- 6.5 7.3 7.9
Base** 0.075 7.6 9.0 11.0
AO A plus 0.075
Compound of 0.075 6.4 7.6 9.8
Example 4 of
U.S. 4,318,845
AO A plus 0.075
Example 1 0.075 7.1 7.7 9.1
______________________________________
*Blank contains 0.075% by weight of calcium stearate.
**AO A is neopentanetetrayl
tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).
The instant alpha, monoclinic crystalline compound is particularly
effective in stabilizing polypropylene against discoloration as shown by a
minimum change in the yellowness index in the presence of a representative
phenolic antioxidant and is equal or more effective that the prior art
compound of U.S. Pat. No. 4,318,845.
EXAMPLE 6
Stabilization of Unsaturated Elastomer
The instant compound of Example 1 is evaluated in an emulsion of SBR (cold
polymerized, 23.5% styrene with a 52 Mooney Viscosity). The unstabilized
SBR (60 g) is added to the mixing chamber of a Brabender Plasticorder set
at 150.degree. C. and 60 rpm. After 30 seconds, 0.5% by weight of the
compound of instant Example 1 is added to the chamber. Stability of the
SBR is determined by the time until onset of crosslinking of the rubber as
indicated by an increase in the torque curve. The sample stabilized by the
instant compound has a longer induction time till crosslinking occurs than
does the unstabilizer SBR.
EXAMPLE 7 cl Stabilization of Polyol
A premix of 10 g of water, 0.25 g of triethylenetetramine, 2 g of L-5740
(silicone surfactant, Union Carbide) and 20 g of ANTIBLAZE.RTM. AB-100
(chlorinated aromatic flame retardant, Albright & Wilson) is added to 200
g of 3000 molecular weight polyether polyol containing the stabilizer
package listed below*. The mixture is stirred for five minutes with a high
speed Lightning Mixer. Then 0.4 g of stannous octoate is added and the
mixture is stirred for 5 seconds. Finally, 125 g of toluene diisocyanate
(80% 2,6-isomer, 20% 2,4-isomer) is added. The mixture is stirred for 7
seconds at high speed mixing and is then poured into a 10".times.5" (25.4
cm.times.25.4 cm.times.12.7 cm) cardboard box. The foam is allowed to rise
completely. After standing 5 minutes, the box is removed and the sample
cured in a microwave over for five minutes at 50% power. The foam is then
immediately air over cured at 125.degree. C. for three minutes. The foams
are then cut in half for visual assessment of discoloration or scorch.
*Stabilizer package:
Control is 2,6-di-tert-butyl-4-methylphenol (BHT) 2000 ppm; and
NAUGARD.RTM. 445 (diphenylamine antioxidant, Uniroyal) 2000 ppm.
Instant package is the above plus 1000 ppm of the compound of Example 1.
Visual inspection of the two foams shows that the foam containing the
instant stabilizer package with the compound of Example 1 present is less
discolored than the foam stabilized with the control stabilizer package.
The instant compound demonstrates better scorch protection.
EXAMPLE 8
Stabilization of Polycarbonate
Additive free bisphenol A polycarbonate (LEXAN.RTM. 141-111N, General
Electric) is dried and blended with 0.3 weight percent of a benzotriazole
UV absorber CHNUVIN.RTM. 329, Ciba-Geigy) and 0.08 weight percent of
instant compound of Example 1. The mixture is extruded and pelletized at
550.degree. F. (288.degree. C.) on a 1" (2.54 cm) single screw extruder.
Injection molded plaques (2".times.2".times.125 mil; 5.08 cm.times.5.08
cm.times.3.175 mm) are prepared in a BOY 30M injection molder at
560.degree. F. (293.degree. C.) with a mold temperature of 150.degree. C.
The resulting plaques are measured for yellowness index (YI) using ASTM D
1925-70. The plaques containing the instant compound of Example 1 have a
lower YI values than those containing the UV absorber alone demonstrating
the better performance achieve by the concomitant presence of the instant
phosphite.
EXAMPLE 9
Stabilization of Poly(ethylene terephthalate)
Poly(ethylene terephthalate), PET (KODAPAR.RTM. 7352, Eastman Chemical) is
tumble blended with 0.5% by weight of the compound of instant Example 1.
The polymer is then extruded and pelletized at 500.degree. F. (260.degree.
C.) in a MPM 1" (2.54 cm) single screw extruder. The pellets are
collected, redried and reextruded 5 times. Pellets are collected from each
extrusion pass and the polymer intrinsic viscosity measured. PET
containing the instant compound of Example 1 shows a higher retention of
original intrinsic viscosity through the five extrusion passes than does
PET containing no stabilizer.
EXAMPLE 10
Stabilization of Poly(butylene terephthalate)
Poly(butylene terephthalate), PBT (RYNITE.RTM. 9160, DuPont) is tumble
blended with 0.3% by weight of the compound of instant Example 1. The
polymer is then extruded and pelletized at 260.degree. C. A portion of the
collected pellets are reextruded under the same conditions for a second
pass. The remainder from the first extrusion is injection molded into
2".times.2".times.125 mil (5.08 cm.times.5.08 cm.times.3.175 mm) plaques
at 540.degree. F. (282.degree. C.) with a 100.degree. C. mold temperature
in a BOY 30M molder. Intrinsic viscosities of the second pass extrudate
and the injection molded plaques are determined. The PBT containing the
instant compound of Example 1 shows a better retention of intrinsic
viscosity value than does PBT containing no stabilizer.
The plaques are measured for yellowness index (color) using ASTM D1925-70.
The plaques containing the instant compound of Example 1 have a lower YI
values (less discoloration) than do the plaques prepared from the control
unstabilized PBT.
EXAMPLE 11
Stabilization of 6,6-Nylon
6,6-Nylon (ZyTEL.RTM. 101, DuPont) is thoroughly dried in a vacuum oven and
tumble blended with 0.5% by weight of the compound of instant Example 1.
The polyamide is extruded on a 1" (2.54 cm) MPM extruder at 575.degree. F.
(302.degree. C.). The collected pellets are injection molder at
575.degree. F. (302.degree. C.) with the mold at 150.degree. C. in a BOY
30M injection molder. The plaques obtained are measured for yellowness
index (YI) values using ASTM D1925-70. The plaques containing the instant
compound of Example 1 exhibit lower YI values (less discoloration) than do
the unstabilized control plaques.
EXAMPLE 12
Stabilization of ABS
A solution of 0.25 g of the instant compound of Example 1 in 40 ml of
hexane/methanol is added to a rapidly stirred suspension of 100 g of ABS
(acrylonitrile/butadiene/styrene terpolymer) in 600 g of water. The
suspension is filtered and dried under vacuum at 40.degree. C. for 40
hours. To the dried powder is added 2% by weight of titanium dioxide and
1% by weight of N,N'-ethylenebisstearamide on a two roll mill at
180.degree. C. over four minutes. Compression molded plaques (0.8 mm) are
prepared at 175.degree. C. and placed in an air oven at 180.degree. C. for
45 minutes. The color of said plaques are determined as yellowness index
values using ASTM D1925-70. The plaques containing the instant compound of
Example 1 exhibit lower yellowness index values (less discoloration) than
do the control plaques from unstabilized ABS resin.
EXAMPLE 13
X-ray Analysis
The procedure for the X-ray analysis performed here is the same as provided
in instant Example 1.
The x-ray analyses of the two compounds listed below are carried out to
show that the alpha, monoclinic crystalline form is distinctly different
from the prior art compound of U.S. Pat. No. 4,318,845.
Compound A=alpha crystalline form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'-diyl)phosphite!, prepared in accordance with instant Example 1 and
recrystallized from ethyl acetate.
Compound B=Spivack form of
2,2',2"-nitrilo triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,
2'diyl)phosphite!, prepared in accordance with Example 4 of U.S. Pat. No.
4,318,845. The product was recrystallized from a mixture of acetonitrile
and toluene.
______________________________________
Property Compound A Compound B
______________________________________
Melting Point 160.degree. C.
134-140.degree. C.
Unit Cell Dimensions
a 20.0700 .ANG.
20.308 .ANG.
b 17.477 .ANG. 17.615 .ANG.
c 27.620 .ANG. 27.918 .ANG.
.beta. 93.050.degree.
93.730.degree.
Volume 9674.5 .ANG..sup.3
9966 .ANG..sup.3
Density (calc) 1.006 Mg/m.sup.3
0.986 Mg/m.sup.3
______________________________________
Comparison of the data readily shows a difference in structure between the
instant alpha crystalline form (Compound A) and the prior art Spivack
compound (Compound B).
The unit cell of Compound B contains an entrapped molecule of toluene. This
was not recognized by Spivack et al., and the Spivack reference fails to
mention this. In contrast, the crystal cell of Compound A does not contain
a molecule of solvent from any of the claimed recrystallization solvent
systems.
The above fact is clearly reflected in the large difference in melting
points between the alpha crystalline form (Compound A) and the prior an
material (Compound B). Additionally, this fact is seen in comparing the
difference between the cell dimensions, volume and density. In particular,
a significant difference can be seen by comparing the volumes of the alpha
crystalline form (9674.5 .ANG..sup.3) and the prior an material (9966
.ANG..sup.3). The X-my diffraction data clearly distinguish the structure
of the instant compound (that is, the alpha crystalline form) from that of
the prior an Spivack compound.
EXAMPLE 14
Solubility in LLDPE Film at Various Temperatures
Experiments are carried out to determine the solubility of the instant
compound into linear low density polyethylene (LLDPE) films at 20.degree.
C., 40.degree. C. and 60.degree. C. by diffusion-in of a relatively
homogeneous particle size (<70 microns) of the test sample suspended in
silicon oil.
Each sample is carefully ground with a mortar and pestle and the particle
size below 70 microns is separated by sieving with a 200 mesh screen. The
powder is then suspended in silicon oil (polydimethylsiloxane, L-45, Union
Carbide Chemicals) at a concentration of approximately 38% (wt/wt). A few
drops of this suspension is placed on a 10 mil (0.254 mm) thick,
2".times.2" (5.08 cm.times.5.08 cm) compression molded film and a second
film of the same dimension is placed on top. The films are gently pressed
together so that the suspension forms a thin liquid layer between the
polymer films. Excess suspension is removed and the procedure is repeated
till a stack of eight films (six films for evaluation) are prepared. The
stack is then placed between two 2.5".times.2.5" (6.35 cm.times.6.35 cm)
ceramic tiles and wrapped in aluminum foil and held together with a
G-clamp. Each stack is aged at 20.degree. C., 40.degree. C. and 60.degree.
C. under a nitrogen atmosphere. At specified intervals, a single film is
removed from the stack and the excess suspension is washed from the film
with hexane. The film is then analyzed by X-ray fluorescence for total
phosphorus content. I J-DPE containing 0, 1000 ppm and 2000 ppm of the
test compound are used as standard controls for this X-ray fluorescence
method.
The solubility data are given in the Table below.
______________________________________
Solubility of Compound in LLDPE at 20.degree. C.
ppm
Compound of 15 28 35 44
______________________________________
Example 4 of 1500 1000 1200 1200
U.S. 4,318,845
instant 2000 1000 1200 1500
Example 1
______________________________________
Solubility of Compound in LLDPE at 40.degree. C.
ppm
10 17 25 34 40 47
______________________________________
Example 4 of
500 1750 750 400 600 1400
U.S. 4,318,845
instant 1000 1750 800 1100 1100 950
Example 1
______________________________________
Solubility of Compound in LLDPE at 60.degree. C.
ppm
6 14 22 28 37
______________________________________
Example 4 of
1000 800 1000 900 900
U.S. 4,318,845
instant 2000 1900 1900 2000 2200
Example 1
______________________________________
It is clear from these data that the instant alpha, monoclinic crystalline
compound of Example 1 is somewhat more soluble in LLDPE than is the prior
art compound of Example 4 of U.S. Pat. No. 4,318,845.
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